CN103804782A - Non-halogen flame retardant resin composition, and wire and cable using the same - Google Patents
Non-halogen flame retardant resin composition, and wire and cable using the same Download PDFInfo
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- CN103804782A CN103804782A CN201310348740.XA CN201310348740A CN103804782A CN 103804782 A CN103804782 A CN 103804782A CN 201310348740 A CN201310348740 A CN 201310348740A CN 103804782 A CN103804782 A CN 103804782A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a non-halogen flame retardant resin composition which has excellent mechanical features of stretching strength and extension, and properties of flame retardance, flexibility, and water resistance, and a wire and a cable using the same. The non-halogen flame retardant resin composition comprises a polymer and 180-250 parts by mass of non-halogen flame retardant, and the polymer contains 10-30 parts by mass of polypropylene, ethylene, 4-10 parts by mass of ternary polymer containing ethylene, alpha olefin with polar group, and maleic anhydride, and 54-86 parts by mass of polyolefin resin, which is composed of 100 parts by mass in total.
Description
Technical field
The present invention relates to non-halogen fire-retardancy resin combination and use its electric wire, cable.
Background technology
As the flame retardant resin composition of halogen contained compound not, use the composition that has added the metal hydroxides such as magnesium hydroxide, aluminium hydroxide in polyolefin-based resins.These compositions are owing to not producing the toxic gases such as hydrogenchloride, dioxin in when burning, the generation of the poisonous gas therefore can prevent fire time, prevent secondary disaster etc.And, do not have problem even if carry out incineration process when discarded yet.But compared with existing halogenated flame retardant, by adding, the flame retardant effect that brings of metal hydroxides is little, can not obtain as the situation of the flame retardant resistance of object a lot, therefore the addition of metal hydroxides is carried out to increment.
For the increment of the addition of above-mentioned metal hydroxides, exist mechanical characteristics significantly to reduce such problem points thereupon.For example, the mechanical characteristics such as tensile strength, elongation extremely reduces along with the interpolation of metal hydroxides.Therefore, generally adopt the crystallinity of polymkeric substance self high, as the polypropylene (below sometimes referred to as PP) of high-strength polymer.But PP can not contain the weighting agents such as metal hydroxides in a large number, therefore adds the elastomerics that the crystallinity such as EVA are low, make to contain weighting agent in this elastomerics.
But PP and elastomerics are generally difficult to compatible, can not mix by homogeneous even if therefore admix merely, usually can not show good characteristic.Therefore,, so that two polymer-compatible turn to object, add terpolymer.As such terpolymer, generally use non-polar polymkeric substance by the group modified polymkeric substance of sour isopolarity, particularly, disclose and used by the composition of maleic anhydride modified ethylene copolymer (for example, with reference to patent documentation 1).
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-19190 communique
Summary of the invention
The problem that invention will solve
But, in the inventor's etc. research, use in polymer-modified situation as described above as terpolymer, be difficult to improve the introduction volume of polar group, the therefore for example less addition below 10 mass parts, can not obtain enough effects.Therefore, known PP and elastomeric compatible insufficient, the extreme reduction of the volume specific resistance while showing dipping.In addition, if increase polymer-modified addition, in polymkeric substance, PP and elastomeric ratio reduce, the excellent tensile strength that therefore PP has and elongation, the reduction such as flexibility and weighting agent acceptability that also has elastomerics to have.
Therefore, the object of the present invention is to provide the non-halogen fire-retardancy resin combination of mechanical characteristics, flame retardant resistance, flexibility and the water tolerance excellences such as a kind of tensile strength, elongation, and use its electric wire, cable.
The scheme of dealing with problems
The inventor etc. are in order to reach above-mentioned purpose, through concentrating on studies, result is thought by the compatibility agent as polypropylene and polyolefin-based resins, use ethene, there is the alhpa olefin of polar group and the terpolymer of maleic anhydride, can toxilic acid be used for to modification, but therefore one of raw material when synthetic as polymkeric substance can improve the amount of toxilic acid in polymkeric substance.Thus, discovery can obtain a kind of polymkeric substance consistency each other and improve, the non-halogen fire-retardancy resin combination of the mechanical characteristicies such as tensile strength, elongation, flame retardant resistance, flexibility and water tolerance excellence, thus complete the present invention.,, according to the present invention, following non-halogen fire-retardancy resin combination is provided and has used its electric wire, cable.
[1] a kind of non-halogen fire-retardancy resin combination, it contains polymkeric substance and non-halogenated flame retardant 180～250 mass parts, described polymkeric substance comprises polypropylene 10～30 mass parts, ethene, there are the alhpa olefin of polar group and the ter-polymers of maleic anhydride 4～10 mass parts, and polyolefin-based resins 54～86 mass parts except polypropylene, by adding up to 100 mass parts to form.
[2], according to the non-halogen fire-retardancy resin combination aforementioned [1] Suo Shu, wherein, as D type hardness tester meter hardness, there is 50～60 hardness, and the volume specific resistance flooding after 30 days is 1.0 × 10 in 80 ℃ of warm water
10more than Ω cm.
[3], according to the non-halogen fire-retardancy resin combination aforementioned [1] or [2] Suo Shu, wherein, aforementioned polyolefin-based resins is that vinyl acetate content (VA amount) is 20～45% ethylene-vinyl acetate copolymer.
[4] according to the non-halogen fire-retardancy resin combination described in any one in aforementioned [1] to [3], wherein, aforementioned ter-polymers is the ter-polymers of ethylene-propylene acetoacetic ester-maleic anhydride.
[5] electric wire, it has: conductor; With the isolator that uses the formation of the non-halogen fire-retardancy resin combination coating described in any one in aforementioned [1] to [4] in aforementioned conductor periphery.
[6] cable, it has: the isolator and the sth. made by twisting many wires together that have respectively conductor and form in aforementioned conductor periphery coating; The compacting part of reeling in the periphery of aforementioned sth. made by twisting many wires together; Sheath with the non-halogen fire-retardancy resin combination coating formation described in any one in the periphery of aforementioned compacting part is used aforementioned [1] to [4].
Invention effect
According to the present invention, the non-halogen fire-retardancy resin combination of mechanical characteristics, flame retardant resistance, flexibility and the water tolerance excellences such as a kind of tensile strength, elongation is provided, and uses its electric wire, cable.
Accompanying drawing explanation
Fig. 1 be pattern the sectional view of the cable that embodiments of the present invention relate to (have respectively copper conductor and the isolator forming in its periphery coating and the outer periderm writing that surpasses all the others band of twisting with the fingers many wires together and the cable of sheath coating) is shown;
Fig. 2 be pattern the sectional view of the electric wire that embodiments of the present invention relate to (having copper conductor and the electric wire of the isolator that forms in its periphery coating) is shown.
Description of reference numerals
1: copper conductor; 2: isolator; 3: sheath; 4: be situated between at thing; 5: writing that surpasses all the others band.
Embodiment
[embodiment summary]
For the non-halogen fire-retardancy resin combination relating to for present embodiment, containing in the non-halogen fire-retardancy resin combination that comprises polyolefin-based resins and polyacrylic polymkeric substance and non-halogenated flame retardant, contain polymkeric substance and non-halogenated flame retardant 180～250 mass parts, described polymkeric substance comprises polypropylene 10～30 mass parts, ethene, there are the alhpa olefin of polar group and the ter-polymers of maleic anhydride 4～10 mass parts, and polyolefin-based resins 54～86 mass parts except polypropylene, by adding up to 100 mass parts to form.
[embodiment]
Below, the non-halogen fire-retardancy resin combination to present embodiment and use it for isolator or the electric wire of sheath, cable describe.
I. non-halogen fire-retardancy composition
The non-halogen fire-retardancy resin combination of present embodiment contains polymkeric substance and non-halogenated flame retardant 180～250 mass parts, described polymkeric substance comprises polypropylene 10～30 mass parts, ethene, there are the alhpa olefin of polar group and the ter-polymers of maleic anhydride 4～10 mass parts, and polyolefin-based resins 54～86 mass parts, by adding up to 100 mass parts to form.Below each composition is described particularly.
1. polymkeric substance
The polymkeric substance that present embodiment is used is configured to as mentioned above and comprises polypropylene, ethene, has the alhpa olefin of polar group and the terpolymer of maleic anhydride, and polyolefin-based resins.
(polypropylene)
(PP) that form polymkeric substance is generally roughly divided into homopolymerization PP (homopolymer of propylene), random PP and block PP.
As random PP, for example, can enumerate ethylene-propylene random copolymer, alhpa olefin-random copolymer of propylene.As block PP, can enumerate Ethylene-Propylene Block Copolymer, alhpa olefin-propylene copolymer.In addition, in block PP, also comprise that polypropylene chains and ethylene-propylene copolymer chain do not have the material of chemical bonding.Be not particularly limited as the PP using in present embodiment, but preferred block PP.They,, as long as within the limits prescribed, just can be used alone or mixed use of two or more.
Polyacrylic addition is 10～30 mass parts.If discontented 10 mass parts can not obtain enough tensile strengths, if exceed 30 mass parts, elongation reduction, also hardening of hardness, can not be applicable to electric wire, cable.
(polyolefin-based resins)
As the polyolefin-based resins that forms polymkeric substance, for example can enumerate Low Density Polyethylene (LDPE), straight chain shape Low Density Polyethylene (LLDPE), straight chain shape ultra-low density polyethylene (VLDPE), high density polyethylene(HDPE) (HDPE), ethylene-ethyl acrylate copolymer (EEA), ethylene vinyl acetate copolymer (EVA), ethylene-methyl methacrylate glycidyl ester copolymer, ethene-1-Butylene copolymer, ethene-butylene-hexene terpolymer, ethylene-propylene-diene terpolymer (EPDM), ethylene-octene copolymer (EOR), poly--4-methyl-amylene-1, hydrogenated styrene-butadienecopolymer (H-SBR), the multipolymer of the alhpa olefin of ethene and carbonatoms 4～20, ethylene-styrene copolymer etc., they are as long as being just used alone or mixed use of two or more within the limits prescribed.
Be not particularly limited as polyolefin-based resins, preferably EVA, further preferably vinyl acetate content (VA amount) is the EVA of 20～45 % by weight.
The addition of polyolefin-based resins is 54～86 mass parts.If discontented 54 mass parts, the PP addition in polymkeric substance becomes too much, and elongation characteristic reduces, if exceed 86 mass parts, the tensile strength of the PP in polymkeric substance reduces.
(terpolymer)
As form polymkeric substance ethene, there is the alhpa olefin of polar group and the terpolymer of maleic anhydride is not particularly limited.As the alhpa olefin with polar group, can enumerate there is acryl, the alkene of acyl group isopolarity group, more specifically, can enumerate ethyl propenoate, methyl acrylate, butyl acrylate, vinyl acetate etc.In addition, as the applicable example of terpolymer, can enumerate ethene, ethyl propenoate and maleic anhydride.
The addition of terpolymer is 4～10 mass parts.If discontented 4 mass parts, PP and polyolefin-based resins is compatible insufficient, and water tolerance reduces, if exceed 10 mass parts, elongation characteristic reduces.
2. non-halogenated flame retardant
As the non-halogenated flame retardant using in present embodiment, for example can enumerate the metal hydroxidess such as magnesium hydroxide, aluminium hydroxide, calcium hydroxide, trimeric cyanamide, cyanuric acid, tricarbimide, melamine cyanurate, sulfuric acid trimeric cyanamide etc. 1,3,5-pyrrolotriazine derivatives, the zn cpdss such as zinc, zinc hydroxyl stannate, zinc borate, zinc oxide; The boronic acid compounds such as lime borate, barium borate, barium metaborate; Phosphorus flame retardant; Expansion (the イ Application テ ュ メ ッ セ Application ト) flame retardant that the mixture of the composition foaming during by burning and curing composition forms etc.These can be used alone or mixed use of two or more.
In addition, for these fire retardants, can use by silane coupling agent, titanic acid ester is that lipid acid or the fatty acid metal salt etc. such as coupling agent, stearic acid or calcium stearate have carried out surface-treated fire retardant.
The addition of non-halogen fire-retardancy resin combination is 180～250 mass parts.If discontented 180 mass parts, can not obtain enough flame retardant resistances, if exceed 250 mass parts, elongation characteristic significantly reduces.
3. other additives
In the non-halogen fire-retardancy resin combination of present embodiment, except above-mentioned polymkeric substance and non-halogenated flame retardant, also can coordinate as required the additives such as oxidation inhibitor, metal passivator, linking agent, crosslinking coagent, lubricant, inorganic filler, compatibility agent, stablizer, carbon black, tinting material.Further, also can utilize organo-peroxide to be cross-linked, or utilize electron beam isoradial to be cross-linked.
Be not particularly limited as oxidation inhibitor, for example can enumerate phenol is that oxidation inhibitor, sulphur are that oxidation inhibitor, amine are, phosphorus is oxidation inhibitor etc.Be that oxidation inhibitor is not particularly limited as phenol, for example can enumerate butylated hydroxytoluene (BHT), tetramethylolmethane four [3-(3,5-bis--tert-butyl-hydroxy phenyl) propionic ester], 1,3,5-tri-(3,5-bis--tertiary butyl-4-hydroxy-benzyl)-guanamine, 4,6-(1H, 3H, 5H) triketone, sulfo-di ethylene bis [3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester] etc., preferably tetramethylolmethane four [3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester].
Be that oxidation inhibitor is not particularly limited as sulphur, for example can enumerate two dodecyls 3,3 '-thiodipropionate, double tridecyl 3,3 '-thiodipropionate, two octadecyl 3,3 '-thiodipropionate, four [methylene radical-3-(dodecyl sulfo-) propionic ester] methane etc., preferably four [methylene radical-3-(dodecyl sulfo-) propionic ester] methane.
Be that oxidation inhibitor is not particularly limited as amine, for example can enumerate 6-oxyethyl group-1, 2-dihydro-2, 2, 4-trimethylquinoline, phenyl-1-naphthalene, alkylated diphenylamine, octylated diphenylamine, 4, 4 '-bis-(α, α-dimethylbenzyl) pentanoic, 2, 2, 4-trimethylammonium-1, 2-dihydroquinoline polymkeric substance, to (para toluene sulfonamide) pentanoic, N, N '-bis--2-naphthyl-Ursol D, N, N '-phenylbenzene-Ursol D, N-phenyl-N '-sec.-propyl-Ursol D, N-phenyl-N '-(1, 3-dimethylbutyl)-Ursol D, N-phenyl-N '-(3-methacryloxy-2-hydroxypropyl)-Ursol D, 1, two [2-(1-oxo-2-phenoxy propyl) hydrazides of 3-benzene dicarboxylic acid, 2 ', the two [[3-[3 of 3-, 5-bis--tert-butyl-hydroxy phenyl] propionyl]] propionyl hydrazine, 3-(N-salicylyl amino)-1H-1, 2, 4-triazole, dodecanedioic acid two [N2-(2-hydroxy benzoyls) hydrazides] etc.
These oxidation inhibitors can be used alone or mixed use of two or more.
For metal passivator; thereby have by forming inner complex and make metal ion stabilization, the deteriorated effect of inhibited oxidation; be not particularly limited as its structure; can enumerate N-(2H-1; 2; 4-triazole-5-yl) salicylic amide, dodecanedioic acid two [N2-(2-hydroxy benzoyl) hydrazides], 2 '; the two [[3-[3 of 3-; 5-bis--tert-butyl-hydroxy phenyl] propionyl]] propionyl hydrazine etc.; preferably 2 '; 3-two [[3-[3,5-bis--tert-butyl-hydroxy phenyl] propionyl]] propionyl hydrazine.
Be not particularly limited as crosslinking coagent, for example, can enumerate trimethylolpropane trimethacrylate (TMPT), triallyl isocyanurate (TAIC) etc.
Be not particularly limited as lubricant, for example, can enumerate lipid acid, fatty acid metal salt, fatty acid amide etc., can enumerate particularly Zinic stearas etc.They can be used alone or mixed use of two or more.
Be not particularly limited as inorganic filler, for example, can enumerate clay, talcum, silica etc.They also can utilize the surface treatment agent such as lipid acid, silane to carry out surface treatment.They can be used alone or mixed use of two or more.
Be not particularly limited as carbon black, for example, can enumerate the carbon black (N900-N100:ASTM D1765-01) that rubber is used.
Be not particularly limited as tinting material, for example, can enumerate colour batch that non-halogen uses etc.
And the non-halogen fire-retardancy resin combination of present embodiment, from the viewpoint such as flexibility and water tolerance, preferably has 50～60 hardness as D type hardness tester meter hardness, and flood 30 in 80 ℃ of warm water after, volume specific resistance is 1.0 × 10
10more than Ω cm.
II. electric wire
The electric wire of present embodiment as shown in Figure 2, has copper conductor 1, and uses the isolator 2 of above-mentioned non-halogen fire-retardancy resin combination coating formation and form in the periphery of copper conductor 1.
III. cable
The cable of present embodiment as shown in Figure 1, has: the isolator 2 and the sth. made by twisting many wires together that have respectively copper conductor 1 and form in the periphery coating of copper conductor 1; In the periphery of twisting with the fingers many wires together, with compacting part, for example writing that surpasses all the others band 5(signature さ え Juan テ ー プ that for example paper Jie reels together with thing 4); Form with the sheath 3 that uses above-mentioned non-halogen fire-retardancy resin combination coating to form in the periphery of writing that surpasses all the others band 5.In this situation, isolator 2 preferably uses above-mentioned non-halogen fire-retardancy resin combination to make.Embodiment
Below, use embodiment further to illustrate to non-halogen fire-retardancy resin combination of the present invention and electric wire, cable.And the present invention is not subject to any restriction of following examples.
(embodiment 1)
Coordinate polyethylene company of PP(Japan to manufacture, trade(brand)name: BC8A) 10 mass parts, EVA(vinyl acetate content (VA amount): 25 % by weight, MFR:2.0) 84 mass parts, (Arkema manufactures ethylene-propylene acetoacetic ester-copolymer-maleic anhydride, trade(brand)name: Bondine LX4110) 6 mass parts, (Shen Dao chemical company manufactures magnesium hydroxide, trade(brand)name: Magseeds S6), hindered phenol is that (BASF Japanese firm manufactures oxidation inhibitor, trade(brand)name: Irganox1010) 1.0 mass parts and sulphur is that (ADEKA company manufactures oxidation inhibitor, trade(brand)name: AO-412S) 0.5 mass parts, adopt pressurization kneader 40 ℃ of starting temperatures, after mixing at 190 ℃ of end temps, mixing thing (non-halogen fire-retardancy resin combination) is made granular.
The making of electric wire is carried out in the following way, the mixing thing as shown in Figure 2, above-mentioned employing pressurization kneader being obtained is extruded according to the mode that becomes electric wire external diameter 0.98mm, the thick 0.25mm of isolator at 200 ℃ of design temperatures in the periphery of copper conductor 1 and as isolator 2.
The making of cable is carried out in the following way, as shown in Figure 1, by 3 of said wires and paper be situated between thing 4 is common twist with the fingers together with, apply writing that surpasses all the others band 5 thereon, extrude the above-mentioned employing pressurization kneader of coating and the mixing thing that obtains and as sheath 3 in its periphery.
The gradation composition of the non-halogen fire-retardancy resin combination using in embodiment 1 is shown in table 1, and meanwhile, the evaluation result of aftermentioned electric wire is shown in table 1.
(embodiment 2～13)
The gradation composition of non-halogen fire-retardancy resin combination is become to the composition shown in table 1, in addition carry out similarly to Example 1.The evaluation result of electric wire is shown in to table 1.
(comparative example 1～10)
The gradation composition of non-halogen fire-retardancy resin combination is become to the composition shown in table 2, in addition carry out similarly to Example 1.The evaluation result of electric wire is shown in to table 2.
(evaluation method of electric wire)
The evaluation of electric wire is judged by method shown below.
(1) tension test
The electric wire of making is carried out to tension test according to JIS C3005.Elongation discontented 150% be × (defective), 150～300% be zero (qualified), more than this, be ◎ (have more than needed qualified).The discontented 10MPa of tensile strength be × (defective), and 10～13MPa's is zero (qualified), is ◎ (have more than needed qualified) more than this.
(2) flame retardant test
Carry out the testing vertical flammability (VW-1) under electric wire shape.For judgement, discontented 30 seconds of combustion time be ◎ (have more than needed qualified), 30 seconds above discontented 1 minute be zero (qualified), 1 minute above is × (defective).
(3) hardness test
The sample of lamella shape is carried out to hardness test according to JIS K6253.Use D type hardness tester meter to measure, below 60 is zero (qualified), be greater than 60 for × (defective).
(4) volume specific resistance
The 1mm thin slice of making was flooded after 30 days in the warm water of 80 ℃, measure volume specific resistance.Volume specific resistance is measured according to JIS K6271.1 × 10
13more than Ω cm is ◎ (have more than needed qualified), 1 × 10
10Ω cm is discontented with 1 × 10 above
13Ω cm's is zero (qualified), discontented 1 × 10
10Ω cm is × (defective).
As shown in table 1, in embodiment 1～13, the tension test in table, flame retardant test, hardness test, in water tolerance test, any characteristic is all good result.In embodiment 1,2, although changed the addition of PP, have the PP tendency that tensile strength reduces at least, elongation improves, be good characteristic under 10～30 mass parts of regulation.In embodiment 3～4, although changed ethene, there is the addition of the alhpa olefin of polar group and the terpolymer of maleic anhydride, there is addition water tolerance slight reduction, the addition tendency that elongation characteristic reduces at most at least, but be good characteristic under 4～10 mass parts of regulation.In embodiment 3,5～8, although changed polyolefin-based resins, be all good characteristic.In addition, use flame retardant resistance raising compared with using the embodiment 6～8 of other polymkeric substance of the embodiment 3,5 of the EVA of VA amount 20～45 % by weight as polyolefin-based resins, the viewpoint improving from flame retardant resistance, it is preferred using the EVA of VA amount 20～45 % by weight.In embodiment 9～10, although changed the addition of non-halogenated flame retardant, have the tendency that flame retardant resistance improves along with the increase of addition, be good characteristic under 180～250 mass parts of regulation.In addition, embodiment 11 has added melamine cyanurate as non-halogenated flame retardant, and compared with un-added embodiment 6, flame retardant resistance improves, and from the viewpoint of flame retardant resistance, interpolation is preferred.In embodiment 12, added lubricant, inorganic filler, tinting material, added lubricant, inorganic filler, carbon black in embodiment 13, characteristic is good.
On the other hand, as shown in table 2, the tensile strength of the comparative example 1 that the addition of PP is fewer than regulation is inadequate.The elongation characteristic of the comparative example 2 that in addition, the addition of PP is more than regulation is inadequate.The water tolerance of ethene, comparative example 3 that the addition with the alhpa olefin of polar group and the terpolymer of maleic anhydride is fewer than regulation is inadequate, and addition is more inadequate than the elongation characteristic that stipulates many comparative examples 4.Use the comparative example 5～6 of toxilic acid MODIFIED PP and use the comparative example 7～8 of toxilic acid modified PE in the situation of any addition as terpolymer, all water tolerance is inadequate.The flame retardant resistance of the comparative example 9 that the addition of fire retardant is fewer than regulation is inadequate, and the elongation characteristic of the comparative example 10 more than regulation is inadequate.
Table 1
Table 2
Claims (6)
1. a non-halogen fire-retardancy resin combination, it contains polymkeric substance and non-halogenated flame retardant 180～250 mass parts, described polymkeric substance comprises polypropylene 10～30 mass parts, ethene, there are the alhpa olefin of polar group and the ter-polymers of maleic anhydride 4～10 mass parts, and polyolefin-based resins 54～86 mass parts except polypropylene, by adding up to 100 mass parts to form.
2. non-halogen fire-retardancy resin combination according to claim 1, wherein, as D type hardness tester meter hardness, have 50～60 hardness, and the volume specific resistance flooding in 80 ℃ of warm water after 30 days is 1.0 × 10
10more than Ω cm.
3. non-halogen fire-retardancy resin combination according to claim 1 and 2, wherein, described polyolefin-based resins is that vinyl acetate content is that VA amount is 20～45% ethylene-vinyl acetate copolymer.
4. according to the non-halogen fire-retardancy resin combination described in any one in claims 1 to 3, wherein, described ter-polymers is the ter-polymers of ethylene-propylene acetoacetic ester-maleic anhydride.
5. an electric wire, it has:
Conductor; With
The isolator that non-halogen fire-retardancy resin combination coating in described conductor periphery right to use requires 1 to 4 described in any one forms.
6. a cable, it has:
The isolator that there is respectively conductor and form in described conductor periphery coating and sth. made by twisting many wires together;
The compacting part of reeling in the periphery of described sth. made by twisting many wires together; With
The sheath that non-halogen fire-retardancy resin combination coating in the periphery right to use of described compacting part requires 1 to 4 described in any one forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012241554A JP5765316B2 (en) | 2012-11-01 | 2012-11-01 | Non-halogen flame retardant resin composition and electric wire / cable using the same |
| JP2012-241554 | 2012-11-01 |
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| CN103804782A true CN103804782A (en) | 2014-05-21 |
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| CN201310348740.XA Pending CN103804782A (en) | 2012-11-01 | 2013-08-12 | Non-halogen flame retardant resin composition, and wire and cable using the same |
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| JP7140028B2 (en) * | 2019-03-28 | 2022-09-21 | 日本ポリエチレン株式会社 | Flame-retardant resin composition, electric wire and cable |
| WO2021241682A1 (en) | 2020-05-28 | 2021-12-02 | 三菱ケミカル株式会社 | Resin composition and molded body |
| CN116061502B (en) * | 2023-03-28 | 2023-06-06 | 山东寿光鲁清石化有限公司 | Material for high-density polyethylene silicon core tube |
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| US5073590A (en) * | 1988-10-15 | 1991-12-17 | Sumitomo Chemical Company, Limited | Themoplastic resin composition and process for producing the same |
| JPH06283030A (en) * | 1993-03-25 | 1994-10-07 | Hitachi Cable Ltd | Nonflammable electric insulating composite and insulated wire |
| CN101174492A (en) * | 2006-10-10 | 2008-05-07 | 日立电线株式会社 | Non-halogen fire resistant wire with excellent process at ends |
| CN101319072A (en) * | 2006-08-16 | 2008-12-10 | 住友橡胶工业株式会社 | Electroconductive thermoplastic elastomer composition, its manufacturing method and molded product |
| CN101323689A (en) * | 2007-06-13 | 2008-12-17 | 日立电线株式会社 | Non-halogen flame retardant resin composition and non-halogen flame retardant electric wire and cable |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06290638A (en) * | 1993-03-30 | 1994-10-18 | Hitachi Cable Ltd | Flame-resistant electric insulating composite and insulated wire using the composite |
| JP3068422B2 (en) * | 1993-11-12 | 2000-07-24 | 古河電気工業株式会社 | Insulated wire |
| JP5516303B2 (en) * | 2010-10-07 | 2014-06-11 | 日立金属株式会社 | Insulated wire and manufacturing method thereof |
-
2012
- 2012-11-01 JP JP2012241554A patent/JP5765316B2/en active Active
-
2013
- 2013-08-12 CN CN201310348740.XA patent/CN103804782A/en active Pending
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|---|---|---|---|---|
| US5073590A (en) * | 1988-10-15 | 1991-12-17 | Sumitomo Chemical Company, Limited | Themoplastic resin composition and process for producing the same |
| JPH06283030A (en) * | 1993-03-25 | 1994-10-07 | Hitachi Cable Ltd | Nonflammable electric insulating composite and insulated wire |
| CN101319072A (en) * | 2006-08-16 | 2008-12-10 | 住友橡胶工业株式会社 | Electroconductive thermoplastic elastomer composition, its manufacturing method and molded product |
| CN101174492A (en) * | 2006-10-10 | 2008-05-07 | 日立电线株式会社 | Non-halogen fire resistant wire with excellent process at ends |
| CN101323689A (en) * | 2007-06-13 | 2008-12-17 | 日立电线株式会社 | Non-halogen flame retardant resin composition and non-halogen flame retardant electric wire and cable |
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| 姚祝平: "《塑料挤出成型工艺与制品缺陷处理》", 31 May 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014091753A (en) | 2014-05-19 |
| JP5765316B2 (en) | 2015-08-19 |
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Application publication date: 20140521 |